CN114870889B - Ru-RuO 2 -Nb 2 O 5 Bimetallic catalyst and preparation method and application thereof - Google Patents
Ru-RuO 2 -Nb 2 O 5 Bimetallic catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a Ru-RuO 2 ‑Nb 2 O 5 Bimetallic catalyst and its preparation method and application. The high activity of Ru and the stability of Nb are based on the selection of noble metals Ru and niobium oxide with low content as active components, and active species are controlled at an atomic level by a co-impregnation preparation method, so that Ru-RuO is controlled 2 ‑Nb 2 O 5 Is synthesized in the catalyst. The interface catalyst is used for efficiently preparing cyclohexanol by low-temperature hydrogenation of phenol and lignin oil monomer derivatives, and has good hydrogenation activity.
Description
Technical Field
The invention belongs to the field of catalysts, and in particular relates to a Ru-RuO 2 -Nb 2 O 5 Bimetallic catalyst and its preparation method and application.
Background
Cyclohexanol is an important intermediate in the synthesis of a variety of organic chemicals. Cyclohexanol can be produced by catalytic oxidation of cyclohexane and subsequent hydrogenation. However, cyclohexane is not economically advantageous for the production of cyclohexanol as a high value-added paraffinic substance. In recent years, many studies have shown that lignin can be selectively depolymerized into aromatic monomers by various methods such as pyrolysis, hydrolysis, hydrogenolysis, hydrogenation, and oxidation. The lignin component in the biomass is depolymerized to obtain a bio-oil non-volatile fraction (lignin oil) containing a large amount of oxygen-containing aromatic monomers. The method for producing the cyclohexanol with high added value by directly catalyzing and hydrogenating the lignin oil in the biological oil has important significance in the aspects of reducing cost and utilizing waste lignin.
In the prior art for preparing cyclohexanol by hydrogenating aromatic hydrocarbon monomers, hydrogenation catalysts mainly comprise transition metals and noble metals. The former is often used because of its low cost and wide source, with nickel-based transition metals being preferred. However, the hydrogenation activity of the transition metal is generally lower than that of the noble metal, and the reaction condition is more severe. According to the previous reports, it was found that the catalytic activity of the nickel catalyst is directly affected by the dispersion of the metal sites, the size of the nickel nanoparticles and the geometry of the nanoparticles.
Among noble metal catalysts, noble metal catalysts have received attention because of their high hydrogenolysis ability and aromatic ring hydrogenation ability under mild reaction conditions. Although noble metals have excellent hydrogenation capabilities, sources are scarce and expensive, and activity is affected by particle size and geometry. Therefore, the coupling of low-content noble metal and transition metal is used as an active catalyst for low-temperature high-efficiency hydrogenation, and the coupling of low-content noble metal and transition metal is a preferred catalyst for preparing cyclohexanol by low-temperature hydrogenation of oxygenated aromatic hydrocarbon based on economic cost and high activity.
Disclosure of Invention
The primary purpose of the invention is to overcome the defects and shortcomings of the prior art and provide a Ru-RuO 2 -Nb 2 O 5 A preparation method of a bimetallic catalyst.
Another object of the present invention is to provide Ru-RuO prepared by the above method 2 -Nb 2 O 5 Bimetallic catalysts.
It is still another object of the present invention to provide the Ru-RuO as described above 2 -Nb 2 O 5 Bimetallic catalysisApplication of the agent.
The aim of the invention is achieved by the following technical scheme:
Ru-RuO 2 -Nb 2 O 5 The preparation method of the bimetallic catalyst comprises the following steps:
(1) Adding a ruthenium-containing compound and a niobium-containing compound into a solvent, stirring and dissolving, adding a carrier, continuously stirring, and drying to obtain a dried mixed precursor.
(2) Heating and reducing the dried mixed precursor to obtain Ru-RuO 2 -Nb 2 O 5 Bimetallic catalysts.
The ruthenium-containing compound in step (1) is a soluble ruthenium salt; ruthenium acetate is preferred.
The niobium-containing compound described in step (1) is niobium hydroxide.
The ruthenium-containing compound and the niobium-containing compound described in step (1) are added in an amount of 0.3 to 1:1 to 3, preferably 0.3, in terms of the ratio of the molar mass of ruthenium in the ruthenium-containing compound to the molar mass of niobium in the niobium-containing compound: 2.
the carrier in the step (1) is a molecular sieve, preferably an H beta molecular sieve, more preferably an H beta molecular sieve calcined at 550 ℃.
The ratio of the mass of the support described in step (1) to the molar mass of niobium in the niobium-containing compound is 1 to 3:1 to 3, preferably 1:1.
The solvent in the step (1) is absolute ethyl alcohol.
The solvent in the step (1) is added in such an amount that the niobium-containing compound and the ruthenium-containing compound can be dissolved.
The stirring continuing time in the step (1) is 1-3 h; preferably 1h.
The temperature of the drying in the step (1) is 60-100 ℃; preferably 80 ℃.
The heating and reduction in the step (2) is performed by using a tube furnace.
The heating and reduction in the step (2) are carried out until the temperature is between 500 and 700 ℃; preferably 600 ℃.
The heating rate of the heating reduction in the step (2) is 5-10 ℃/min; preferably 10 deg.c/min.
The heating and reduction in the step (2) are performed under a reducing atmosphere, preferably a hydrogen/nitrogen atmosphere, more preferably a 10% hydrogen 90% nitrogen mixed atmosphere.
The hydrogen pressure of the reducing atmosphere is 0-4 MPa, preferably 2MPa.
The heating and reducing time in the step (2) is 0-2 h, but not 0; preferably 1h.
Ru-RuO 2 -Nb 2 O 5 The bimetallic catalyst is obtained by the preparation method.
Ru-RuO as described above 2 -Nb 2 O 5 The application of the bimetallic catalyst in catalytic hydrogenation reaction.
Ru-RuO as described above 2 -Nb 2 O 5 The application of the bimetallic catalyst in catalyzing the hydrogenation reaction of aromatic hydrocarbon.
Preferably, the aromatic hydrocarbon is one or more of lignin-derived substrates.
Preferably, the aromatic hydrocarbon is at least one of phenol, eugenol, anisole and benzyl ether.
Preferably, the aromatic hydrocarbon is a mixed substrate comprising phenol, anisole and benzyl ether.
Preferably, the molar ratio of phenol, anisole and benzyl ether in the mixed substrate is 1-2:1-2, and more preferably 1:1:1.
Preferably, the reaction condition of the hydrogenation reaction is that the hydrogen pressure is 0-4 MPa, the temperature is 30-120 ℃ and the time is 5 min-24 h; the hydrogen pressure is more preferably 2MPa,120℃and 8 hours.
Preferably, the addition amount of the catalyst in the hydrogenation reaction is 2-6% (w/w) of the mass of the substrate.
Preferably, the solvent used in the hydrogenation reaction is decalin.
Preferably, the Ru-RuO 2 -Nb 2 O 5 The bimetallic catalyst was 0.3% Ru2% Nb-H2 beta.
Compared with the prior art, the invention has the following advantages and effects:
the invention provides a Ru-RuO 2 -Nb 2 O 5 Bimetallic catalyst and its preparation method and application. The high activity of Ru and the stability of Nb are based on the selection of noble metals Ru and niobium oxide with low content as active components, and active species are controlled at an atomic level by a co-impregnation preparation method, so that Ru-RuO is controlled 2 -Nb 2 O 5 Is synthesized in the catalyst. The interface catalyst is used for efficiently preparing cyclohexanol by low-temperature hydrogenation of phenol and lignin oil monomer derivatives, and has good hydrogenation activity.
Drawings
FIG. 1 is Ru-RuO 2 -Nb 2 O 5 Schematic of catalyst synthesis.
FIG. 2Ru-RuO 2 -Nb 2 O 5 And a graph of the effect on phenol hydrogenation.
Fig. 3H 2 And the effect of pressure on phenol hydrogenation.
FIG. 4 is a graph of the effect of reaction time on phenol hydrogenation; wherein A is 0.3% Ru2% Nb-H BETA; b is 0.3% Ru-H BETA.
FIG. 5 is a graph showing the effect of reduction time on the hydrogenation effect of a catalyst during the catalyst preparation process.
Detailed Description
EXAMPLE 1 preparation of Ru-Nb/Hbeta catalysts with different Nb contents
Catalyst preparation
40mg of ruthenium acetate and 170.14mg of niobium hydroxide are weighed according to a proportion, placed in a beaker, the specific proportion is that the molar ratio of ruthenium to niobium is 1:1, and then 5ml of absolute ethyl alcohol is added to stir until the ruthenium acetate and the niobium hydroxide are completely dissolved, so as to obtain a precursor. Then adding 2g of H beta molecular sieve calcined at 550 ℃ and stirring for 1H continuously, so that the precursor is completely and uniformly mixed and dispersed on the surface and pores of the H beta molecular sieve to obtain the mixed precursor. After drying in an oven at 80 ℃, the mixed precursor was transferred to a quartz tube using a tube furnace at 10% h 2 /N 2 Heating to 600 ℃ at a heating rate of 10 ℃/min in the flow, and reducing for 1 hour to obtain Ru-RuO loaded by H beta zeolite 2 -Nb 2 O 5 Bimetallic interface catalyst 0.3% Ru2%Nb-Hβ.
With reference to the preparation method, the ruthenium-niobium molar ratio of the raw materials of ruthenium acetate and niobium hydroxide is adjusted to be 0.3:0.3 (40 mg:25.52 mg), 0.3:1 (40 mg:85.07 mg), 0.3:3 (40 mg:255.21 mg), and other preparation steps are the same, so that the bimetallic interface catalyst of 0.3% RuNb-H beta, 0.3% Ru1% Nb-H beta and 0.3% Ru3% Nb-H beta is prepared.
With reference to the preparation method, the single metal catalyst for comparison of the preparation effect comprises 0.3% Ru-H beta and 2% Nb-H beta, wherein the difference is that only 40mg ruthenium acetate or 170.14mg niobium hydroxide is added into the raw materials.
Example 2 procedure for phenol hydrogenation and evaluation of catalyst reaction
1. Step of phenol hydrogenation reaction
Reaction conditions: 2mmol phenol, 0.05g catalyst, 20mL decalin, reaction temperature 30 ℃, initial H 2 The pressure is 2.0MPa, and the reaction time is 9h.
The specific operation steps are as follows:
(1) A weighing balance weighed 50mg of catalyst into a quartz liner, 2mmol of phenol was added, and 20ml of decalin solvent was added.
(2) Adding magnetic stirrer, placing the lining into the kettle, packaging, checking gas and liquid valve switch, and connecting thermocouple.
(3) Introducing hydrogen, sealing, waiting for 5min, observing the air tightness again, and discharging the hydrogen.
(4) And (5) introducing hydrogen again, and discharging the residual gas in the kettle.
(5) And finally, introducing hydrogen required by the reaction, and sealing. The reaction kettle is opened, the conditions of reaction temperature, reaction time, rotating speed and the like are set, and the reaction is carried out for 9 hours at 30 ℃ under the condition of hydrogen pressure of 2MPa by magnetic stirring at 800 rpm.
(6) After the reaction is finished, cooling to room temperature, discharging gas, and collecting liquid products.
(7) Chromatographic testing was performed after filtration using an organic 13mm x 0.22um filter head.
2. Detection of product and evaluation of catalyst reaction
After filtration through 13mm x 0.22um organic filters, the liquid product species of the product were analyzed by testing with a gas chromatograph-mass spectrometer (Thermo Trace 1300-ISQ) equipped with a TG-5MS chromatographic column (30 m x 0.25mm x 0.25 μm). The products were quantitatively tested by using a gas chromatograph (Agilent) with the same capillary column. The temperature-raising program is as follows: hold at 40℃for 5min, then raise to 280℃at a rate of 10℃per min for 3min.
The detection results are shown in FIG. 2. The phenol had 0% and 6.54% hydroconversions of 2% Nb-H.beta.and 0.3% Ru-H.beta.respectively. Single Nb 2 O 5 The phenol has no hydrogenation activity and may not trap hydrogen or form active hydrogen protons. The monometal ruthenium has a relatively low capacity to capture hydrogen at room temperature and therefore has a weak hydrogenation effect on phenol. When Nb is gradually added to 0.3% Ru-Hβ, the conversion of phenol by hydrogenation is markedly improved. When the Nb content was increased from 0% to 2%, the conversion of phenol was increased from 7.88% to 100%. When the Nb content reached 3%, the phenol conversion remained at 100%, indicating that the active sites of the catalyst were not affected by the Nb excess. The main product was cyclohexanol, with selectivity to cyclohexanol increased from 4.04% to 98.28% as the Nb content in the catalyst increased from 0 to 2%. The results show that Ru-RuO 2 -Nb 2 O 5 The interface plays an important role in the benzene ring hydrogenation process.
Example 3 optimization of conditions for phenol hydrogenation
1. Investigation of H using 0.3% Ru2% Nb-H beta catalyst 2 The effect of pressure on phenol hydrogenation.
Reaction conditions: 2mmol phenol, 0.05g 0.3% Ru2% Nb-H beta catalyst, 20mL decalin as solvent, 30℃reaction temperature, 9H reaction time.
Specific operation steps refer to example 2, except that the hydrogen pressure in step (5) was set to 0, 0.5, 1, 2, 4MPa, respectively.
The resulting product was detected using the detection method of example 2, and the results are shown in FIG. 3. With increasing hydrogen pressure, the hydrogenation performance of phenol is significantly improved. When the hydrogen pressure was 2Mpa, the conversion of phenol was 100%, and the cyclohexanol selectivity was 98%. When the hydrogen pressure is lower than 1Mpa, the phenol conversion of 0.3% ru2% nb-hβ is lower than 10%. Further increasing the hydrogen pressure to 4Mpa, the phenol conversion and the cyclohexanol selectivity were both 100%, and cyclohexanone disappeared.
2. To further investigate the specific conversion process of phenol in the catalyst, the effect of reaction time on phenol hydrogenation was investigated using the catalysts 0.3% Ru2% Nb-H BETA and 0.3% Ru-H BETA.
Reaction conditions: 2mmol phenol, 0.05g catalyst, 20mL decalin, H 2 The pressure is 2MPa, the temperature is 30 ℃, and the reaction time is 24 hours.
Specific procedure referring to example 2, the difference was that the catalysts were tested using 0.3% Ru2% Nb-H-BETA and 0.3% Ru-H-BETA, respectively, and the reaction was performed in-line in an autoclave with continuous sampling test for 24 hours.
The resulting product was detected using the detection method of example 2, and the results are shown in FIG. 4. The results show that the phenol conversion at the same time is much faster than 0.3% Ru2% Nb-H.beta.s (FIG. 4A) than 0.3% Ru-H.beta.s (FIG. 4B). In the initial stage, phenol is first converted to equal amounts of cyclohexanol and cyclohexanone. The phenol was then completely converted to cyclohexanol after 4 hours. When the reaction time reached 12h, the c=o bond of cyclohexanone began to be hydrogenated to cyclohexanol. By observing the conversion profile of 0.3% Ru-H.beta.it was found that phenol was also converted to cyclohexanol and cyclohexanone simultaneously in the initial stage. However, cyclohexanone is far more selective than cyclohexanol. The selectivity of cyclohexanol began to exceed that of cyclohexanone at 8 hours, the cyclohexanone reaction reached equilibrium, and after 8 hours the reaction had not progressed further toward cyclohexanol.
Example 4 different lignin derived substrates in Ru-RuO 2 -Nb 2 O 5 Hydrogenation over catalyst
(1) Reaction a:2mmol of substrate (one of eugenol, anisole and benzyl ether), the catalyst is added in an amount of 4% (w/w) of the substrate, 20mL of decalin, and initial H 2 The pressure is 2MPa, the temperature is 30 ℃, the reaction is carried out for 9 hours, and the catalyst is used: 0.3% Ru2% Nb-H BETA.
(2) Reaction b:2mmol of substrate (anisole or benzyl ether), 4% (w/w) of catalyst, 20mL of decalin, initial H 2 The reaction is carried out for 9 hours at the pressure of 2MPa and 60 DEG CCatalyst: 0.3% Ru2% Nb-H BETA.
(3) Reaction c: the substrate is mixed substrate phenol 1mmol, anisole 1mmol and benzyl ether 1mmol, the addition amount of the catalyst is 8% (w/w) of the substrate, decalin 20mL and the initial H 2 The pressure is 2MPa, the temperature is 120 ℃, the reaction is carried out for 9 hours, and the catalyst is used: 0.3% Ru2% Nb-H BETA.
For specific procedures, reference is made to example 2.
TABLE 1 Ru-RuO 2 -Nb 2 O 5 Catalyst in decalin for evaluating hydrogenation reaction of different lignin derivative substrates
This example investigated the hydrogenation of different lignin-derived substrates over 0.3% Ru2% Nb-H beta catalyst and the results are shown in Table 1. Anisole, benzyl ether and eugenol were hydrogenated at 30℃at 28.07%, 43.04% and 17.69% conversion, respectively. The elevated reaction temperature significantly increased the hydrogenation activity of anisole and benzyl ether (Table 1, numbered 3-5). For example, when the reaction temperature was raised to 60 ℃, the conversion of anisole was raised to 54.73%, and the product selectivities of methoxycyclohexane and cyclohexanol were 34.60% and 20.13%, respectively. Likewise, when the temperature was increased from 30 ℃ to 60 ℃, the conversion of benzyl ether increased from 43.04% to 72.79%, (oxybis (methylene)) dicyclohexyl process selectivity increased from 10.79% to 67.83%.
Subsequently, the hydrogenation capacity of 0.3% Ru2% Nb-H2 beta catalyst on mixed substrates (phenol, benzyl ether and anisole) was investigated. The results showed that the conversion of the mixed substrate at 120℃was 100% (Table 1, no. 6), and the selectivity for cyclohexane was highest (32.01%).
Example 5 reduction time affects the effect of catalyst interface on phenol hydrogenation
1. Catalyst preparation
A0.3% Ru2% Nb-Hβ -t catalyst having a Ru content of 0.3% by weight and a Nb content of 2% by weight was prepared by referring to the experimental procedure of example 1. The difference is that the times for carrying out the reduction reaction are set to 5min, 30min, 1H and 2H, respectively, and the obtained catalyst is named as 0.3% Ru2%Nb-H BETA-5 min, 0.3% Ru2%Nb-H BETA-30 min, 0.3% Ru2%Nb-H BETA-1H and 0.3% Ru2%Nb-H BETA-2H.
2. Evaluation of catalyst reaction
Reaction conditions: the substrate is 2mmol phenol, the catalyst is added in an amount of 4% (w/w) of the substrate, 20mL decalin, 30 ℃ and H 2 The pressure is 2.0MPa, and the reaction time is 9 hours.
For specific procedures, reference is made to example 2.
Example to investigate the reduction time pair obtained Ru-RuO during catalyst preparation 2 -Nb 2 O 5 The catalyst with different reduction time is prepared under the influence of the interfacial hydrogenation activity of the catalyst. The reactivity of the catalyst was determined by phenol at 30℃and 2MPa H 2 Is examined under hydrogenation conditions. The results are shown in FIG. 5. The hydrogenation activity of the interfacial catalyst on phenol gradually increases with increasing reduction time. When the reduction time was 30min, the conversion of phenol was only 77.66% and the selectivity of cyclohexanol and cyclohexanone was 62% and 15.66%, respectively. This is mainly due to Ru-RuO formed in the catalyst 2 -Nb 2 O 5 The interface content is low. When the reduction time exceeds 1h, the conversion rate of phenol reaches 100%, and the yield of cyclohexanol reaches more than 90%. This indicates Ru-RuO 2 -Nb 2 O 5 The interface requires a certain reduction time to form stably.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. Ru-RuO 2 -Nb 2 O 5 The preparation method of the bimetallic catalyst is characterized by comprising the following steps:
(1) Adding a ruthenium-containing compound and a niobium-containing compound into a solvent, stirring and dissolving, adding a carrier, continuously stirring, and drying to obtain a dried mixed precursor;
(2) Heating and reducing the dried mixed precursor to obtain Ru-RuO 2 -Nb 2 O 5 A bimetallic catalyst;
the ruthenium-containing compound in the step (1) is ruthenium acetate;
the niobium-containing compound in step (1) is niobium hydroxide;
the carrier in the step (1) is a molecular sieve;
the solvent in the step (1) is absolute ethyl alcohol;
the stirring continuing time in the step (1) is 1-3 h;
the temperature of the drying in the step (1) is 60-100 ℃;
the heating and reduction in the step (2) are carried out until the temperature is 500-700 ℃;
the heating rate of the heating reduction in the step (2) is 5-10 ℃/min;
the heating and reduction in the step (2) are carried out under a reducing atmosphere;
the hydrogen pressure of the reducing atmosphere is 0-4 MPa;
the time of the heating reduction in the step (2) is 0 to 2 hours, but not 0.
2. Ru-RuO according to claim 1 2 -Nb 2 O 5 A bimetallic catalyst characterized by:
the addition amounts of the ruthenium-containing compound and the niobium-containing compound described in the step (1) are 0.3 to 1:1 to 3 in terms of the ratio of the molar mass of ruthenium in the ruthenium-containing compound to the molar mass of niobium in the niobium-containing compound.
3. Ru-RuO according to claim 1 2 -Nb 2 O 5 A bimetallic catalyst characterized by:
the ratio of the mass of the carrier in the step (1) to the molar mass of niobium in the niobium-containing compound is 1-3:1-3.
4. A Ru-RuO according to any one of claims 1 to 3 2 -Nb 2 O 5 The application of the bimetallic catalyst in catalytic hydrogenation reaction.
5. Ru-RuO according to claim 4 2 -Nb 2 O 5 The application of the bimetallic catalyst in catalytic hydrogenation is characterized in that:
the substrate of the catalytic hydrogenation reaction is aromatic hydrocarbon.
6. Ru-RuO according to claim 5 2 -Nb 2 O 5 The application of the bimetallic catalyst in catalytic hydrogenation is characterized in that:
the aromatic hydrocarbon is at least one of phenol, eugenol, anisole and benzyl ether.
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